Unsaturated amides of oxybis (benzenesulfonic acid)

ABSTRACT

WHEREIN R1 is a C2-C12 alkenyl radical wherein the terminal carbon atom has two hydrogen atoms and is bonded to the penultimate carbon atom by means of a double bond; and R2 is a R1 radical, a C1-C6 alkyl radical, a phenyl radical or hydrogen.   Unsaturated amides of oxybis(benzenesulfonic acid), particularly the mono, di, tri and tetraallyl or methallyl amides, are useful as cross-linking agents for polymeric materials, or as monomers or comonomers in producing allylic-type resins. Such unsaturated amides may be represented by the formula:

United States Patent 1 Blackwood et al.

[451 Apr.3,1973

[54] UNSATURATED AMIDES OF OXYBIS (BENZENESULFONIC ACID) [75] Inventors:John C. Blackwood, Melrose; Edwin 0. Hook, Marshfield; Walter Beck, pBedford, all of Mass. [73] Assignee: Stepsan Chemical Company,Northfield, ll].

[22] Filed: Sept. 15, 1971 211 App]. No.: 180,850

[52] US. Cl...;....260/556 AR, 260/75 S, 260/77.5 R, 260/79.3 MU, 260/79.3 R, 260/78 SC,

-260/79.5 C, 260/456 P, 260/556 H,

204/159.l4, 204/l59.15, 204/l59.l6,

204/ 159.17 [51] Int. Cl...- ..C07c 143/78 [58] Field of Search..260/556 AR [56] References Cited UNITED STATES PATENTS 3,234,1902/1966 Tashlick ..260/7 93 MU 3,359,193 12/1967 Pinner ..204/159.17

Primary Examiner' l-lenry R. Jiles Assistant Examiner-S. D. WintersAttorney-Richard P. Crowley et al.

[57] ABSTRACT Unsaturated amides of oxybis(benzenesulfonic acid),particularly the mono, di, tri and tetraallyl or methallyl amides, areuseful as cross-linking agents for polymeric materials, or as monomersor comonomers in producing allylic-type resins. Such unsaturated amidesmay be represented by the formula:

7 Claims, No Drawings UNSATURATED AMIDES OF OXYBIS (BENZENESULFONICACID) BACKGROUND OF THE INVENTION shrinkage and distortion, can usuallybe enhanced in this manner. Cross-linking may also augment the chemicalresistance of the polymer, especially against the action of varioussolvents, and often serves to modify significantly the physicalcharacteristics of the polymer or shaped articles made therefrom. Forexample, a given polymeric composition that normally is relativelyflexible or elastic can often be stiffened considerably by cross-linkingthe polymer. This stiffening can often be accomplished after the polymerhas been formed into a shaped article. Thus, a thermoplastic polymer canbe fabricated by conventional techniques, such as molding or extrusioninto a desired form; e.g., rod, film, etc., while in an easily workable,plastified condition, and later, in such form or another, can beexpediently cross-linked to produce a desirably stiff, rigid and highmelting shaped or molded article.

Cross-linking agents containing unsaturated radicals, such as two ormore unsaturated groups; e.g., allyl groups, are often employed toimprove the physical and chemical properties of various polymers. Suchwell known cross-linking agents as triallyl cyanurate, triallylphosphite, diallyl phthalate, trimethylolpropane trimethacrylate andother di and tri-functional compounds, are employed to improve theperformance of polymers to provide highly cross-linked polymericstructures of improved stiffness at elevated temperatures and enhancedheat resistance (see U.S. Pat. No. 3,359,193). The cross-linking agentreaction with polymers is a typical vinyl polymerization reaction whichis carried out in the presence of a free-radical generating catalystsystem, such as a peroxide, or azonitrile catalyst, or by the use ofradiation or any combination thereof.

Oxybis(benzenesulfonyl hydrazide) is a commercially produced productused as a blowing agent in rubbers for the production of cellular-rubberproducts (see U.S. Pat. No. 2,626,933 and U.S. Pat. No. 2,552,065). Thisblowing agent is prepared by reacting oxybis(benzenesulfonyl chloride)with hydrazine. The intermediate product, oxybis(benzenesulfonylchloride), is typically prepared by reacting diphenyl oxide withchlorosulfonic acid. The compound produced is a stable but reactiveintermediate compound for the preparation of the blowing agent.

SUMMARY OF THE INVENTION Our invention relates to a new class ofunsaturated cross-linking compounds, their use in cross-linkingpolymers, and in preparing homopolymers and copolymers. Our inventionconcerns unsaturated compounds of oxybis(benzensulfonic acid), inparticular, the unsaturated amides and unsaturated esters ofoxybis(benzene-sulfonic acid), as new compounds of matter. Our inventionalso is directed to the use of these unsaturated oxybis(benzenesulfonyl)compounds, particularly the unsaturated allyl or methallyl amides ofoxybis(benzenesulfonic acid), as cross-linking agents and as additivesin polymers, and as monomers or comonomers in producing allylic-typeresins. More particularly, our invention concerns the di and tetraallylor methallyl amides of oxybis(benzenesulfonic acid), their use inpolymers as cross-linking agents with free-radical generating catalystsystems to enhance the heat resistance and improve the stiffness of thepolymers at elevated temperatures, and their use as monomers andcomonomers in producing high-temperature-resistant allylic-type resins.

The unsaturated compounds of our invention may be represented by theformula (I) wherein R is an unsaturated radical containing, for example,one two, three or more ethylenically unsaturated carbon-to-carbon bonds,and particularly, wherein R contains an olefinic radical wherein theterminal carbon atom bears two hydrogen atoms and is bonded to thepenultimate carbon atom by means of a double bond, for example, anallyl, methallyl, ethallyl or vinyl radical, bonded directly to anintermediate oxygen or nitrogen atom which is bonded to the sulfur atom.

In one embodiment of our invention, R may represent an ester radical (CRand in anotherembodiment of our invention, R may represent anunsaturated amide radical R represents an olefinic-containing radical,such as a radical containing one, two, three or more ethylenicallyunsaturated bonds, subject to cross-linking in the presence of afree-radical generating catalyst system.

R may represent an aliphatic or a cycloaliphatic radical, such as analkenyl C -C, radical, or a vinyl or alkylene-substituted aromaticradical, such as a C C alkylene-substituted phenyl. Preferably, R is a C-C alkenyl radical, such as a vinyl radical, an allyl radical, or a C,-Callyl or phenyl-substituted allyl radical, such as methallyl, ethallyl,propallyl, butylallyl, cyclohexylallyl, or phenylallyl radicals.

R represents the same or a different R radical or hydrogen, or analiphatic, cycloaliphatic, aromatic; e.g., phenyl or alkylaryl; e.g.,alkyl phenyl radical. Preferably, R is a phenyl or C,C., alkyl phenyl ora C,C alkyl radical, such as a methyl, ethyl, propyl, butyl, cyclohexylradical.

The unsaturated esters of oxybis(benz'enesulfonic acid) of our inventionmay be prepared by an esterification reaction through reacting anoxybis( benzenesulfonic acid halide), such as the bromide, chloride,iodide or fluoride, but particularly preferred is the bromide orchloride, with a hydroxy-containing unsaturated compound, such as, forexample, an unsaturated alcohol; e.g., a C -C alkenol, such as allylalcohol or an alkyl-substituted allyl alcohol, such as methallylalcohol, to produce the corresponding allyl or methallyl compounds.Further, unsaturated ester compounds of our invention containing acrylicradicals may be methacryloxyethyl) oxybis(benzene-sulfonate), di(betamethacryloxypropyl) oxybis(benzenesulfonate).

The preferred monomers of our invention for use as cross-linking agentsare the unsaturated amides of the oxybis(benzene-sulfnic acid), sincesuch compounds may contain up to four unsaturated groups therein wherethe nitrogen atom on each end may contain one or two unsaturated groups,and more particularly wherein our compounds are the diallyl andtetraallyl oxybis(benzenesulfonamides).

The unsaturated amides of our invention would include, but not belimited to: diallyl oxybis(benzenesulfonamide),. tetraallyloxybis(benzenesulfonamide), N,N-diallyl-N,N'-dimethyloxybis(benzenesulfonamide), N,N'-diallyl-N,N'-diethyloxybis-(benzenesulfonamide), N,N'-diallyl-N,N'-dibutyloxybis(benzenesulfonamide), dimethallyl oxybis(benzenesulfonamide),tetramethallyl oxybis(benzensulfonamide), N,N'-dimethallyl-N,N'-dimethyloxybis(benzenesulfonamide), N,N-diallylN,N'-diphenyl oxybis-(benzenesulfonamide), N,N-diallyl-N,N'-dicyclohexyloxybis(benzenesulfonamide), N,N'-dimethyl-N,N- divinyloxybis(benzenesulfonamide), N,N'-diethallyl- N,N' dimethyl oxybis(benzenesulfonamide), and N,N- diallyl-N,N'-di-(p-t-butylphenyl)oxybis(benzenesulfonamide).

The unsaturated amides of our represented by the formula (II):

,The particularly preferred compounds to be employed as cross-linkingagents will be those allyl amides containing two, three, or fourunsaturated radicals, such as the di and tetraallyl or methallylcompounds. The amides employed as monomers or comonomers for theproduction of high-temperature-resistant resins may contain from one tofour of the unsaturated groups.

The unsaturated oxybis(benzenesulfonamide) compounds of our inventionmay typically be prepared by: first, reacting a primary or secondaryamine containing the desired unsaturated group with anoxybis(benzenesulfonyl halide), such as the chloride, bromide, fluorideor iodide, preferably, the chloride, to form the correspondingunsaturated amide of the oxybis(benzenesulfonyl) compound, such as, forexample, by the reaction of amono or diallyl amine or a mono or di C --Calkyl-substituted allyl amine with oxybis(benzenesulfonyl chloride) toproduce the corresponding di or tetraallyl amide compound.

invention are Further, the unsaturated amides of our invention may beprepared, for example, by reacting a mono or primary amine with anoxybis(benzenesulfonyl halide) to produce the corresponding disubstitute amide, and then, further substituting the hydrogen atom onthe nitrogen by an unsaturated group by reacting an unsaturated halidewith the di-substituted amide replacing the hydrogen on the nitrogenatom with the unsaturated group. More particularly, the reaction may bethe reaction of a monomethyl, ethyl, propyl, or tertiary butyl monoaminewith oxybis(benzenesulfonyl chloride) to produce the correspondingdi-substituted amide, and then further, reacting this amide with anallyl halide, such as allyl chloride, or an alkyl-substituted allylchloride, to produce the corresponding diallyl or dimethallyldialkyl-substituted amides of our invention. Our unsaturated amides ofoxybis(benzenesulfonyl) compounds may be prepared by carrying out thereaction in bulk or, preferably, in an organic solvent, such as toluene,benzene, tetrahydrofuran, or xylol, with stirring for 10 to 60 minutes.The reaction is exothermic, and typically, the reaction is started outat ambient temperatures such that the reaction temperature ranges from20 to 90 C.

Our unsaturated oxybis(benzenesulfonyl) com- 7 pounds may be employedalone or in combination with other cross-linking agents or otheradditives commonly employed in polymers, such as plasticizers,antioxidants, stabilizers, fillers, pigments, flame retardants,catalysts, etc.. Typically, our compounds may be employed in amountsranging from 0.1 to 30 percent by -weight; for example, 2 to 20 percentby weight, of the polymer. Our cross-linking agents may be employed incombination with triallyl cyanurate, diallyl phthalate, triallylphosphite, trimethylolpropane trimethacrylate, and other cross-linkingagents. Our cross-linking agents may be dispersed, blended, milled,padded, absorbed, impregnated or otherwise added to or incorporated intothe polymer in which they are to be employed as cross-linking agents.For example, the unsaturated oxybis(benzene-sulfonyl) compounds may beadded directly to the polymer or dispersed or solvated in a liquidcarrier or in a plasticizerof said polymer or through a polymer solutionor emulsion, or may be milled or mechanically blended at the desiredconcentration with pellets or powder of the polymer, followed byblending at a temperature above the polymer-softening point.

Our invention also comprises a method of incorporated our cross-linkingmonomers with a synthetic polymer or comonomer that is in substantiallynoncross-linked form, and, thereafter, effecting free-radicalpolymerization and cross-linking of the mixture. Our unsaturatedcompounds employed as cross-linking agents are employed in the presenceof a free-radical generating system, for example, a radiation orperoxide or azonitrile-curing agent as a catalyst.

The free-radical polymerization generally can be induced by known meansfor generating free radicals, such as by radiation or by the use ofperoxide-type or other free-radical chemical additive initiators. In oneprocedure, the free-radical polymerization is effected by exposing theintimately mixed polymer or comonomer and the cross-linking monomer to afield of high energy radiation. However, the free-radical polymerizationcan also be induced through the addition of a free-radical-producingchemical agent to the polymer/cross-linking monomer blend and thesubsequent activation of this initiating agent by the application ofheat to the blend.

Using the method of our invention, shaped polymeric articles arefabricated by forming a composition comprised of a synthetic polymer orcomonomer, our crosslinking monomer, and a free-radical initiator, suchas a peroxide or azonitrile, if one is employed, into the desiredstructure and then effecting free-radical graft polymerization byheating to cross-link the synthetic polymer. This is useful in theproduction of various articles of manufacture which are comprised of thebeneficially cross-linked polymer compositions that have been formedwhile the composition is in a suitably low melting and plasticizedcondition for its optimum workability.

In the method of the present invention, the term polymer refers tosynthetic polymeric materials, such as: vinyl halide resins likepolyvinyl chloride, and copolymers of vinyl chloride with otherunsaturated monomers, such as vinyl acetate; olefinic resins, likepolyethylenes such as the branched low-density (about 0.910 to about0.925) polyethylenes having melting points in the range of 90 to 1 C.,medium and linear high-density polyethylenes made by the Ziegler andPhillips processes, polypropylene, chlorinated polyethylene elastomer,and other C C,, olefin polymers and copolymers; natural and syntheticrubbers, such as cis-polybutadiene, polyisoprene, ethylene-propylene andethylene-propylene diene rubbers, butyl rubber, Neoprene rubber, nitrilerubber, and copolymers of butadiene with styrene and/or acrylonitrile;polyesters such as alkyd resins and polyacrylates and polymethacrylates;nylons, such as the aliphatic Nylons 6, 6/6, 6/10, 12, new aromaticnylons including the polyamide of terephthalic acid and a mixture of2,2,4-and 2,4,4-trimethylhexamethylenediamines, and such experimentalnylons as Nylon 13/13 and Nylon 9; styrene homopolymers and copolymerssuch as styrene-acrylonitrile and ABS resins, acrylic resins,polysulfone resins, amino resins, urethane resins, etc.. Comonomersother than our cross-linking compounds to be employed in our presentinvention include, but are not limited to, diallyl phthalate,polyallyl-containing compounds, such as diallyl succinate, diallyladipate, triallyl cyanurate, as well as other monomers subject topolymerization, such as styrene, acrylic esters and acrylonitrile. Ourcross-linking monomers may be polymerized with these comonomers toproduce a high-temperature-resistant resin.

In carrying out the method of our invention, the cross-linking monomeris thoroughly blended with the synthetic polymer or comonomer. Optimumresults are obtained when the synthetic polymer is in a substantiallyuncross-linked state at the time the components are admixed. Thesynthetic polymer or comonomer and cross-linking monomer may bethoroughly blended by conventional blending techniques, such as by theuse of a differential roll mill, a Banbury mixer or other similarmasticating equipment, or by dry blending the monomer into the powderedpolymer in a ribbon blender or suitable tumbling equipment. Thetemperature of the polymer/cross-linking monomer mixture during theblending procedure is usually not critical provided that the temperatureis not high enough to cause degradation of the polymer or initiatethermal cross-linking. Optimum blending is often obtained when thepolymer is heated to a temperature above its second order transitiontemperature.

The amount of our cross-linking compound to be incorporated in thepolymer or comonomer blend depends upon the specific nature andcharacteristics of the polymer to be cross-linked, the degree ofcrosslinking desired, the cross-linking potency of the particularcross-linking agent that is involved, the transient properties desiredin the uncross-linked composition for purposes of fabrication and thefinal properties desired in the resulting cross-linked composition.Generally, the stiffness or rigidity of a cross-linked compositionincreases with the degree of cross-linkage. Hence, the quantity of thecross-linking compound employed should be chosen to secure the desiredextent of cross-linking, and, therefore, stiffness in the polymericcomposition without induction of excessive brittleness. Generally, asatisfactory result may be achieved when a minor proportion of thecross-linking compound is intimately incorporated in the polymer. Insome instances, very small proportions of the cross-linking agent withsuffice, especially when relatively low levels of crosslinking aredesired in the final product.

It is desirable to utilize such a quantity of the monomer to provide atleast one functional cross-linkage, and conveniently between one and sayabout one hundred functional cross-linkages per every ten thousandcarbon atoms in the chains of the basic polymer. It is frequentlyadvantageous to incorporate an amount of the cross-linking compound inthe polymer that is between about 0.1 and up to about 30 percent byweight, based on the weight of the polymer, but an amount between about2 and 10 percent by weight is usually sufficient for most purposes, andis adapted to produce a wide range of physical properties. When employedwith a comonomer other than the cross-linking compound, the proportionsto be used will be determined by the properties desired in the finalresin product.

The desired cross-linking or graft cross-linking is effected byinitiating free-radical graft polymerization between the cross-linkingmonomer and the synthetic polymer. Preferably, this free-radicalpolymerization is induced by subjecting the plastic composition tohigh-- energy radiation, or by the addition of peroxide or otherfree-radical generating agents.

The high-energy radiation employed to cross-linked the polymercomposition should have an intrinsicenergy greater than the typicalelectron-binding energies of a few electron volts, and be capable ofpenetrating the processed materials. Such high energy and penetration isconveniently available as beta or gamma radiation from, for example,radioactive cobalt, nuclear, reaction fission products and the like.However, if preferred, high-energy radiation from such sources aselectron beam generators, X-ray generators and the like may also beutilized with equivalent benefit. It will usually be expedient to employa high-energy radiation field having an intensity of at least 0.1megarads per hour to avoid unduly long exposure times. Graftcopolymerization or graft cross-linking, under the influence ofhighenergy radiation, may advantageously and quite satisfactorily beconducted at normal room temperatures. Thus, the difficultiesencountered in thermal cross-linking processes, with or withoutcatalysts, are avoided.

The preferred radiation dosage to induce cross-linking is between about1 to 20 megarads, although a greater dosage may be utilized, if it isdeemed necessary. Obviously, greater economic benefits accrue when lowdosages are employed. Thus, in most cases, it is advantageous to employa dosage of 1 to 5 megarads. This is not only economically feasible, butordinarily produces optimum properties and achieves greatest benefit inthe cross-linked products derived from the polymer compositions. Greatlyexcessive dosages should be avoided to prevent degradation ordecomposition of the compositions being cross-linked, especially afterall or substantially all of the cross-linking agent has becomecross-linked in the polymeric composition. Irradiation may be carriedout in a vacuum or in an inert atmosphere, such as a nitrogen gasatmosphere. Irradiation may be done just before addition of ourcross-linking compound and after addition.

In addition to high-energy radiation, chemical freeradical initiatorsmay be employed to effect cross-linking. Chemical free-radicalinitiators are well known and can be employed in the method of thepresent invention to obtain the desired cross-linking between thepolymer and our cross-linking compound. In general, the procedurefollowed for forming cross-linked polymers using chemical free-radicalinitiators is to compound the polymer or comonomer, free-radicalinitiator and cross-linking agent using conventional blending equipmentsuch as Brabender Plastograph, Banbury Mixer or two-roll mill, at atemperature about to 30 C above the softening point of the polymer, butbelow the gel point, for about 5 to minutes. It is also possible to mixthe reactants, preferably in particulate form, at temperatures below thesoftening point of the polymer; e.g., at C, and, thereafter, heat themixture above the softening point of the polymer to form a homogeneousmixture in the molten polymer. It is also sometimes preferred,especially where there is concern with premature cross-linking in themixing or compounding step, to mix solely the polymer and thecross-linking monomer at temperatures at which the polymer is moltenuntil a homogenous mixture is obtained; e.g., about 5 to 20 minutes, andthereafter, add the initiator with continued mixing for an additional 1to 10 minutes. The polymer composition can then be shaped using standardmethods and equipment into films, tubes, wire insulation, moldedarticles and the like. During the forming operation, sufficient heat canbe applied to actuate the free-radical initiator and effect thecross-linking. In an alternate procedure, the free-radicalpolymerization and resultant cross-linking is accomplished bysubsequently curing the shaped material in a mold at a temperature aboveits gel point.

Organic compounds capable of generating free radicals suitable for usein the present invention include azo compounds like azonitriles andazoamides, such as a, a-azobis(isobutyronitrile), a,a'-azobis(cyclohexanecarbonitrile);2-phenylazo-2,4-dimethylvaleronitrile; 2-phenylazoisobutyronitrile;2-phenylazoisobutyramide and the like. Free-radical catalysts may alsoinclude, but not be limited to, peroxides, such as diacyl (e.g., benzoylperoxide, lauroyl peroxide, 2,4- dichlorobenzoyl peroxide); peroxyesters; e.g., tertiary butyl peroxy benzoate, tertiary butyl peroxyacetate, tertiary butyl peroxy isobutyrate; alkyl peroxides; e.g.,ditertiary butyl peroxide, dicumyl peroxide; hydroperoxides; e.g.,tertiary butyl hydroperoxide, cumene hydroperoxide, ketone peroxides;e.g., methylethyl ketone peroxide, acetyl acetone peroxides; as well asdibasic acid peroxides, sulfonylacyl peroxides, peroxy carbonates,peroxy dicarbonates, tertiary alkyl perketals, and the like. The amountof the catalyst used may range from 0.0l to 5 percent by weight of thepolymer; for example, 0.1 to 3.0 percent.

The temperature at which cross-linking of the polymer containing ourunsaturated oxybis(benzenesulfonyl) compound is carried out depends onthe particular catalyst system employed. For ionizing radiation,temperatures of 10 to 50 C may be employed, while for the use ofchemical additives, such as peroxides, the processing temperature toeffect cross-linking is related to the half-life of the catalyst, and,typically, may range from 20 to 150C; for example, 50 to C.

Typically, our cross-linking agents should be compatible with thepolymer into which they are to be incorporated. When employed ascross-linking agents in polymers, our compounds, in part, enhancethermostability of the polymers and produce highly cross-linked andpolymeric structures. Our compounds improve the heat resistance ofpolymers in which they are incor porated, and contribute improvedstiffness at elevated temperatures in such polymers. For example, whenemployed in a vulcanizate, our compounds increase the modulus andtensile strength in comparison to polymers having no cross-linking agenttherein, and reduce the elongation. Our polymers may be used to improvethe adhesion of tire cords when incorporated into adhesive formulationsand to improve the hightemperature physical properties of polymers, andin wire and cable insulation and in hose and belting products.

Also our unsaturated oxybis(benzenesulfonyl) compounds may be employedas monomers and comonomers to produce high-temperature-resistant resins.l-Iomopolymers may be prepared by reacting the unsaturated compounds,such as the tetraallyl oxybis)benzene-sulfonyl amide) compounds, in thepresence of a free-radical generator, such as benzoyl peroxide, andheating to produce the homopolymer, either in solvent or in bulk.Copolymers may be prepared by copolymerizing reaction of, for example,the tetraallylamide compounds with other allyl monomers, such as diallylphthalate, in the presence of a-catalyst, and irradiating to producehigh-temperature allylic-type resins.

For the purposes of illustration only, our invention will be describedby the preparation of unsaturated oxybis(benzenesulfonyl) compounds andtheir use as cross-linking agents in copolymers in the followingexamples.

DESCRIPTION OF THE EMBODIMENTS Example 1 v N,N '-DiallylOxybis(benzenesulfonamide) A solution of 29 g. (0.5 mole) ofmonoallylamine in 100 ml. of toluene was charged to a SOO-cc.round-bottomed flask equipped with a stirrer, thermometer, refluxcondenser, and addition funnel. A solution of 36.7 g. (0.1 mole) ofoxybis(benzenesulfonyl chloride) in 150 ml. of warm toluene was run inover a period of 15 minutes, with vigorous stirring. During theaddition, the temperature of the mixture rose to 75C and slightrefluxing of the amine occurred. When all was in, the reaction productconsisted of a mixture of toluene solution and a pinkishoil.

The mixture was stirred and heated at 7 C for one hour. After 5-10minutes, the oily layer crystallized. Increasing the temperature toabove 80C caused remelting to a heavy amber insoluble syrup. From thisthe toluene solution was decanted while hot, cooled to room temperature,and the resulting slurry filtered, yielding 6 g. of off-white crystals,m.p. 1269C.

The syrupy residue was also cooled to room temperature and treated with300 ml. of cold water, producing a crystalline slurry. This was filteredand the solid product recrystallized from methanol; yield 11.8 g. ofglistening white crystals, m.p. 127-30C. Dilution of the methanolicmother liquor with one-fourth its volume of cold water yielded anadditional 21 g., m.p. 128-30C, bringing the total recovery to 38.8 g.(95 percent of theory).

All of the fractions were combined and recrystallized from methanol (ca.225 ml.), yielding 35.7 g. of product (87.5 percent of theory), m.p.1268C. Example 2' N,N,N',N'-Tetraallyl Oxybis(benzenesulfonamide) To asolution of 49 g. (0.5 mole) of diallyl amine in 100 ml. oftetrahydrofurane in a SOO-cc. reaction flask was added, dropwise andwith good stirring, a solution of 36.7 g. (0.1 mole) ofoxybis(benzenesulfonyl chloride) in 150 ml. of tetrahydrofurane. Theaddition required about 20 minutes, during which the temperature of themixture rose to 63C and amine hydrochloride crystallized out. Tocomplete the reaction, the mixture was stirred and heated under reflux(71C) for 1% hours.

After chilling to 10C, the mixture was filtered and the cake of aminehydrochloride washed with a small amount of chilled tetrahydrofurane.The combined filtrate and washings were concentrated on the hot plate toabout half volume (175 ml.), cooled to room temperature, and treatedwith 500 ml. of cold water. The

' oil which separated crystallized on standing. After several hours inthe refrigerator the mixture was filtered and the product washed wellwith cold water; yield 49 g. (100 percent) of cream-colored solid.Recrystallization from methanol (ca. 225 ml.) yielded 43.7 g. (90percent) of nearly white crystals, m.p. 85-7C. Dilution of the methanolmother liquor with half its volume of cold water produced a 1.8 g.second crop, bringing the total recovery of recrystallized material to93.7 percent of theory.

Example 3.

N,N-Dimethyl-N,N '-Diallyl Oxybis(benzenesulfonamide)" Sodium, 4.6 g.(0.2 mole) was added to 58 g. (1 mole) of allyl alcohol and the mixturestirred and heated at C until the solution of the sodium was complete.35.6 g. (0.1 mole) of oxybis(benzenesulfonyl) dimethylamide was addedand the mixture stirred and heated at C for 10 to 15 minutes, producinga thick, barely stirrable slurry. Allyl chloride, 30.6 g. (0.4 mole),was added slowly through the reflux condenser. Vigorous refluxingoccurred, cooling the mixture to about 60C. The mixture was stirred andheated under reflux at 60C for 2 hours, at which point, the reactiontemperature (initially 60C) had increased to 68C, and the slurry hadbecome much thinner.

After standing overnight, refluxing was continued for an additional hourand a half, at which point the reaction temperature had increased to78C. Two additional hours of reflux resulted in no further change.

The reaction mixture was filtered hot, and the solid precipitate washedwith a small amount of allyl alcohol, and finally with acid. On drying,9% g. (81 percent of theory) of sodium chloride was obtained. The motherliquor was diluted with 200 cc. of cold water and the heavy oil thatseparated taken up in 200 cc. of ether. The ether layer was washed withtwo 50 mls. portions of cold water, and the ether removed under reducedpressure in a rotary evaporator to produce 28.9 g. of viscous amber oil.On treatment of the oil with cold methanol, further chilling andscratching, white crystals were obtained, which, afterrecrystallization, had a melting point of 76 to 80C and an infraredspectrum in agreement with the expected structure.

In this manner, any alkyl-substituted amide of our invention may beprepared; e.g., butyl, ox-

ybis(benzenesulfonamide), wherein the alkyl amine is substituted for theappropriate unsaturated amine, such as a diallyl amine, where theresulting intermediate is an N,N-dialkyl-substituted amineoxybis(benzenesulfonic acid amide) compound, which may then be reactedwith allyl or methallyl chloride to provide the desired introduction ofthe allyl or methallyl groups to replace the hydrogen of the monoalkylamide, thereby yielding an alkyl-substituted allyl sulfonamide of ourinvention. I Example 4 Diallyl oxybis(benzenesulfonate) An excess ofallyl alcohol (2.5 moles) was added to 1.0 moles ofoxybis(benzenesulfonyl chloride) in a flask and the mixture heated toreflux for two hours. The oxybis(benzenesulfonyl chloride) went intosolution at about the boiling point of the allyl alcohol. 0n refluxing,the solution darkened. After refluxing, the excess allyl alcohol wasremoved on a rotary evaporator and a thick reddish-brown oil recoveredas the reaction product. Infrared analysis indicated that the product isthe allyl ester with the concentration of allyl groups about the same asin N,N'-diallyl oxybis- (benzenesulfonamide).

A typical wire and cable polyvinyl-chloride resin formulation wasprepared as follows:

TABLE I Wire and Cable PVC Formulation Percent Parts by Weight 1.Polyvinyl-chloride resin (Geon 102 EP BF Goodrich Chemical Co.) 48.7%400 2. Plasticizer ester of pentaaerythritol (Hercules, Inc.) 21 .3% 1753. Stabilizers dibasic lead,

phthalate, 4.9% 40 lead stearate 0.5% 4 4. Filler treated calciumcarbonate 14.7% 120 5. Antioxidant bisphenol A 0.3% 2.5 6. FlameRetardant antimony trichloride 1.1% 9 7. Cross-linking agent 8.5% 70Totals 100.0% 820.5

In this wire and cable formulation, two cross-linking agents of ourinvention were compared with two commercially known cross-linkingagents; to wit, diallyl phthalate and triallyl cyanurate. The catalystsystem employed comprises exposing the formulation with the variouscross-linking agents to ionizing radiation from a cobalt 60 source inthe dosage as shown in megarads (MR). The irradiated polymer containingthe crosslinking agents was then tested to determine the various degreesof cross-linking effected by the cross-linking agents.

Example One test to illustrate the degree of cross-linking is todetermine the percent elongation at the break point for the variouspolymeric samples. The samples were elongated at a rate of 12 inches perminute, with the reference length being 2 inches. The results of suchelongation test are given in Table II below.

TABLE II Percent Elongation of Irradiated Polymer Broke outsidereference marks The test results in the sample indicate thatcross-linking results achieved with the tetraallyl and diallyloxybis(benzenesulfonamide) compounds of our invention are superior tothose achieved with the use of diallyl phthalate and comparable withthose achieved with triallyl cyanurate.

Example 6.

The polymeric formulation of Table I was again tested after exposure toradiation to determine the degree of cross-linking of the various agentsby measuring the percentage of gel. Percent gel is measured byextraction of weighed samples in tetrahydrofurane to remove solublematerial followed by drying and reweighing. Unirradiated samples of thesame material dissolve almost completely in tetrahydrofurane. The testresults on such irradiated formulation are shown more particularly inTable III wherein a 0 percent gel would represent substantially nocross-linking, and 100 percent gel would represent completecross-linking.

TABLE III Percent Gel of Irradiated Polymer Test No. Percent Gel atRadiation Dosage Cross-linking Agent 1 29% 49% Tetraallyl Oxybis(benzenesul onamide) 2 30% 39% Diallyl Oxybis (benzenesu fonamide) 3 37%42% Diallyl Phthalate 4 56% 63% Triallyl Cyanurate The test results showthat both the tetra and diallyl oxybis(benzenesulfonamide) are effectivecross-linking agents when compared either by percent gel or by percentelongation tests.

Example 7 A cross-linked polyvinyl-chloride formulation as in Table Ihaving improved resistance to high temperature and increased stiffnessat elevated temperatures is prepared by incorporating into theformulation about 15 to 20 phr (parts per hundredparts of resin) ofN-N'- dimethyl-N-N'-diallyl oxybis(benzenesulfonamide), and irradiatingthe formulation in an amount of from about 3 to 5 megarads of radiation.

Example 8 Tetramethallyl oxybis(benzenesulfonamide) is incorporated intoa polyvinyl-chloride resin by the dryblending technique at a level of 25phr. The resulting blend is extruded into rod using extrudertemperatures of 130140C. After irradiation of the samples (2 5 megarads)in a cobalt-60 source, the material is found to be cross-linked, asevidenced by increased softening temperature and insoluble gel fractionsof over 25 percent.

Example 9 The compounds of Examples 1 and 2 are blended with nylon-12 ata level of 15 phr. Blending is accomplished by tumbling the mixture ofnylon-molding pellets and cross-linking monomer in a suitable containeron a set of rolls for 30-60 minutes, or until the pellets are uniformlycoated with the monomer. The blends are then charged to an extruder andprocessed into rod, using extruder temperatures of 380420F. Samples ofthe rod, after irradiation to a dose of 5 megarads, show increases insoftening temperature and elastic modulus (especially at elevatedtemperatures) when compared to unirradiated controls. On extraction'with meta cresol at C, higher insoluble gel contents are found,compared to values for unirradiated controls. Example 10 The products ofExamples 1 and 2 at a level of 10 phr, are incorporated into thefollowing polymers by milling on a heated two-roll mill or masticatingin a Banbury mixer: polypropylene, low and high-density polyethylene,ethylene-propylene rubber, an ethylene/vinyl acetate copolymer',poly(ethyl acrylate), a commercial ABS resin, and an impact grade ofpolystyrene. The products, in the form of molded test bars, areirradiated to a dose of 5 megarads in a cobalt- 60 source. All samplesshow increases in softening tem perature, elastic modulus, and gelcontent after extraction with suitably chosen solvents. Example 1 1 Tothe polyvinyl-chloride resin formulation of Table I, there is addedtwenty-five parts of a tertiary butyl peroxy benzoate as a catalyst,while the cross-linking agent employed is N,N'-dimethyl-N,N'-divinyloxybis(benzenesulfonamide). This formulation is then extruded about acopper wire as wire insulation at an extrusion temperature ofapproximately 140 to 150C, the extruded wire material then chilled andcoiled. Subsequently, the coiled material is again heated to completethe cure in coil form at a temperature of about 130 to 145C for to 40minutes, thereby producing a peroxide-cured cross-linked polyvinylchloride having high-temperature physical properties. Example 12 Diallyloxybis(benzenesulfonate) in an amount of phr is tumbled with powderedlow-density polyethylene (0.92 density), together with 4 phr of benzoylperoxide-curing catalyst until the powdered mixture is intimatelyblended. The mixture is then charged in mass to an extruder, andextruded into a rod-like form at a temperature of approximately 130 to140C. The rod is then subsequently completely cured by heating fromabout five to sixty minutes at a temperature of 130 to 140C in an oven,thereby producing a cross-linked low-density polyethylene havingimproved strength and mechanical properties, as illustrated by decreasedelongation, increased modulus, greater rigidity, and higher gel contentthan the original polyethylene. Example 13 To the PVC resin formulationof Table I, there is incorporated as the cross-linking agent a di(beta)methacryloxyethyl oxybis(benezenesulfonate) and twenty parts of tertiarybutyl peroxy benzoate as a curing catalyst. The formulation is thenmolded into a desired shape and heated at a temperature of 130 to 150 Cfor 5 to 60 minutes to cure the formulation. The cross-linkingpolyvinylchloride resin exhibits evidence of increased rigidity anddecreased elongation as compared to the formulation without thecross-linking agent and catalyst. Example 14 A chlorinated polyethyleneelastomer having enhanced physical properties of a higher modulus and alower elongation and compression set is provided by preparing thefollowing formulation:

Parts by Weight Chlorinated polyethylene elastomer B 100 Lead Stearate 1Dibasic lead phthalate 4 Epoxy resin 2 Carbon black 35 Coated clay 20Chlorinated paraffin 15 Dicumyl peroxide catalyst 2.5 Tetraallyloxybis(benzcnesulfonamide) 4.0

The polymer is cured by heating at a temperature of approximately 150 to165C for 10 to minutes, thereby producing a chlorinated polyethyleneelastomer suitable for use as wire and cable insulation, which elastomerhas an increased tensile strength and reduced elongation than theformulation without our cross-linking agent. Example 15 Ourcross-linking agents provide certain advantages over the employment ofsulfur or other curing agents in elastomers, such as, for example, inethylene-propylene rubber formulations employed as wire and cableinsulation. For example, our cross-linking agent, tetraallyloxybis(benzenesulfonamide), may be incorporated in the amount of 2.5 phrin an ethylene-propylene rubber, such as NJEPR 404 in one hundred parts,and antioxidant 0.75 parts, a secondary antioxidant 0.75 parts,

dicumyl peroxide 7 parts, lead dioxide 3 parts, carbon black 10 parts,treated alumina-silca filler 110 parts and HAF carbon black 40 parts.This formulation on being cured at 15 to minutes at 160C provides anethylene-propylene rubber of low compression set,

good heat-aging stability, improved scorch safety, high modulus andlower elongation than the same formulation cured with 0.3 phr of sulfur.Example 16 Our cross-linking compounds, both the sulfonamides and theester sulfonates, may also be usefully employed in, for example,ethylene-ethyl acrylate copolymers to alter the elongation and modulusproperties of such vulcanizates in a peroxide-cured system. In addition,our cross-linking compounds may also be incorporated into, for example,polyvinylidene fluoride, and cured using a radiation dosage of 4 to 7megarads. In addition, our compounds may be incorporated into highlyunsaturated polyester alkyds to produce resins with improved thermalproperties, as well as being incorporated into phenolics, such asresorcinol formulations employed as tire cord adhesives, or intovinyl-containing polysiloxane resins to react with the vinyl groups ofthe polysiloxane resin to improve the mechanical properties of theresulting resin.

Example 17 An allylic-type copolymer employing our cross-linkingmonomers is prepared, which copolymer is a hightemperature-resistantresin, by mixing 50 parts of the dially oxybis(benzenesulfonamide)compound of Example 2 with 50 parts of diallyl phthalate; heating tosolubilize the mixture at a temperature of about 50 to C, and thenadding to the mixture about 0.5 to 3 parts of a cross-linking agent,azodiisobutyronitrile, and heating the resulting mixture at atemperature of 50 to 60C for about 10 minutes or longer until thematerial copolymerizes into a resinous mass.

Our cross-linking compounds, both the ester and amide compounds, may behomopolymerized by the usual polymerization conditions, or copolymerizedwith a wide variety of vinyl or allyl-containing or other ethylenicallyunsaturated compounds to produce a temperature resistance in resins,particularly the allylic-type temperature-resistant resins.

We claim: v

1. An oxybis(benzenesulfonamide) compound having the formula:

oxybis( benzenesulfon a-

2. The sulfonamide of claim 1 wherein R1 is selected from the groupconsisting of a vinyl radical, allyl radical, or methallyl radical. 3.N,N,N'' ,N''-Tetraallyl oxybis(benzenesulfonamide).
 4. N,N''-Diallyloxybis(benzenesulfonamide).
 5. N,N''-Dimethyl-N,N''-diallyloxybis(benzene-sulfonamide).
 6. N,N,N'' ,N''-Tetramethallyloxybis(benzenesulfonamide).
 7. N,N''-Dimethallyloxybis(benzenesulfonamide).